Journal of Soils and Sediments

, Volume 18, Issue 4, pp 1279–1291 | Cite as

Source indicator of commercial humic products: UV-Vis and fluorescence proxies

  • Olga Yakimenko
  • Daria Khundzhua
  • Aleksei Izosimov
  • Viktor Yuzhakov
  • Svetlana Patsaeva
Natural Organic Matter: Chemistry, Function and Fate in the Environment

Abstract

Purpose

Over the last decades, commercial humic products (HPs) from various resources found multiple applications in agriculture and environmental technologies. The key factor defining chemical properties and biological activity of HPs is their organic matter origin. Thus, there is a need to find diagnostic criteria for differentiating organic sources of HPs. The objective was to determine indicators using absorption and fluorescence spectra in combination with derivative spectroscopy that might serve as tools to compare HPs from various environments, both as bulk materials and their humic acid (HA) fractions.

Materials and methods

HA-like fractions were isolated from commercially available humates, industrially manufactured from a number of raw source materials, such as: fossils (brown coal and leonardite), peat, lake-bottom sediment, and organic waste material (lignosulphonate). They were analyzed using chemical, fluorescence, and UV-Vis measurements. Elemental composition and ash content were determined. The “blue shift” of fluorescence band was defined with excitations at 310 and 270 nm or 355 and 310 nm. The following indices have been calculated from absorption spectra: specific absorbances normalized by the HA content, absorbance ratios E 2:E 3, E 4:E 6, E 270/400 E 280/472, E 280/664, Δ log K, and the spectral slope ratio Sr. In addition, we implement new indices: the ratio of amplitudes in the first-order (FDR280/240) and in the second-order derivative spectra (SDR267/280).

Results and discussion

Absorption spectra of HA-like fractions isolated from HPs varying in organic matter origin demonstrated similar wavelength-dependent character. However, some HA-like fractions demonstrate weak maxima in the derivative spectra with enhanced spectral resolution at 230 and 280 nm. This effect is most probably due to the presence of low molecular weight phenolic compounds, products of lignin decomposition. HA-like fractions isolated from peat- and lignosulphonate-derived HPs show fluorescence maximum at shorter wavelengths than HA-like fractions from coal- and sapropel-derived HPs. Under excitation at 310 nm, certain peat- and lignosulphonate- originated samples manifest significant “blue shift” of emission band. In contrast, HA-like fractions from coal- and sapropel-derived HPs exhibit excitation-independent fluorescence band position or its small shift to longer wavelengths.

Conclusions

Information extracted from absorption and fluorescence spectra can be useful to discriminate organic matter source for HPs from coalified materials (fossils), peat, and lignosulphobate. Indices with the highest descriptive ability, showing strong loadings in principal component analysis, are as follows: specific absorbance SUVA254, absorbance ratios E 270/400, E 280/472, derivative indices FDR280/240 and SDR267/280, wavelength of fluorescence maximum, and the presence of “blue shift”.

Keywords

Absorbance Derivative spectroscopy Fluorescence spectroscopy Humic products Humus acids 

Notes

Acknowledgments

This research was supported by the Russian Foundation for Basic Research (RFBF) No. 15-04-00525_a.

References

  1. Alberts JJ, Takács M (2004) Total luminescence spectra of IHSS standard and reference fulvic acids, humic acids and natural organic matter: comparison of aquatic and terrestrial source terms. Org Geochemistry 35(3):243–356CrossRefGoogle Scholar
  2. Albrecht R, Petit JL, Terrom G, Périssol C (2011) Comparison between UV spectroscopy and NIRS to assess humification process during sewage sludge and green wastes co-composting. Bioresource Technol 102:4495–4500CrossRefGoogle Scholar
  3. Bertoncini EI, D'Orazio V, Senesi N, Mattiazzo ME (2005) Fluorescence analysis of humic and fulvic acids from two Brazilian oxisols as affected by biosolid amendment. Anal Bioanal Chem 381(6):1281–1288CrossRefGoogle Scholar
  4. Burikov SA, Dolenko TA, Kurchatov IS, Patsaeva SV, Starokurov YV (2012) Computer analysis of vibrational spectra of aqueous ethanol solutions. Russ Phys J 55(4):83–388CrossRefGoogle Scholar
  5. Cavani L, Ciavatta C, Gessa C (2003) Identification of organic matter from peat, leonardite and lignite fertilisers using humification parameters and electrofocusing. Bioresource Technol 86(1):45–52CrossRefGoogle Scholar
  6. Chen Y, Senesi N, Schnitzer M (1977) Information provide on humic substances by E4/E6 ratios. Soil Sci Soc Am J 41:352–358CrossRefGoogle Scholar
  7. Chen J, LeBoeuf EJ, Dai S, Gu B (2003) Fluorescence spectroscopic studies of natural organic matter fractions. Chemosphere 50:639–647CrossRefGoogle Scholar
  8. Cory RM, Boyer EW, McKnight DF (2011) Spectral methods to advance understanding of dissolved organic carbon dynamics in forested catchments. In: Levia et al. (eds.), Forest hydrology and biogeochemistry: synthesis of past research and future directions, Ecological studies 216, Springer Science + Business media pp 117–135Google Scholar
  9. Domeizel M, Khalil A, Prudent P (2004) UV spectroscopy: a tool for monitoring humification and for proposing an index of the maturity of compost. Bioresource Technol 94:177–184CrossRefGoogle Scholar
  10. Donard OFX, Lamotte M, Belin C, Ewald M (1989) High-sensitivity fluorescence spectroscopy of Mediterranean waters using a conventional or a pulsed laser excitation source. Mar Chem 27:117–136CrossRefGoogle Scholar
  11. Ertani A, Francioso O, Tugnoli V, Righi V, Nardi S (2011) Effect of commercial lignosulfonate-humate on Zea mays L. metabolism. J Agric Food Chem 59:11940–11948CrossRefGoogle Scholar
  12. Fong SS, Lau IL, Chong WN, Asing J, Faizal M, Nor M, Satirawaty A, Pauzan M (2006) Characterization of the coal derived humic acids from Mukah, Sarawak as soil conditioner. J Braz Chem Soc 17:582–587CrossRefGoogle Scholar
  13. Francioso O, Ciavatta C, Montecchio D, Tugnoli V, Sanchez-Cortes S, Gessa C (2003) Quantitative estimation of peat, brown coal and lignite humic acids using chemical parameters, 1H-NMR and DTA analyses. Bioresource Technol 88:189–195CrossRefGoogle Scholar
  14. Fu P, Wu F, Liu C (2004) Fluorescence excitation-emission matrix characterization of a commercial humic acid. Chin J Geochem 23:309–318CrossRefGoogle Scholar
  15. González Pérez M, Martin-Neto L, Saab SC, Novotny EH, Milori D, Bagnato VS, Colnago LA, Melo WJ, Knicker H (2004) Characterization of humic acids from a Brazilian Oxisol under different tillage systems by EPR, 13C NMR, FTIR and fluorescence spectroscopy. Geoderma 118:181–190CrossRefGoogle Scholar
  16. Gosteva OY, Izosimov AA, Patsaeva SV, Yuzhakov VI, Yakimenko OS (2012) Fluorescence of aqueous solutions of commercial humic products. J Appl Spectroscopy 78(6):884–891CrossRefGoogle Scholar
  17. Helms JR, Stubbins A, Ritchie JD, Minor EC, Kieber DJ, Mopper K (2008) Minor absorption spectral slopes and slope ratios as indicators of molecular weight, source, and photobleaching of chromophoric dissolved organic matter. Limnol Oceanogr 53(3):955–969CrossRefGoogle Scholar
  18. Hemmingsen SL, McGown LB (1997) Phase-resolved fluorescence spectral and lifetime characterization of commercial humic substances. Appl Spectroscopy 51:921–929CrossRefGoogle Scholar
  19. Horst C, Sharma VK, Baum C, Sohn M (2013) Organic matter source discrimination by humic acid characterization: synchronous scan fluorescence spectroscopy and Ferrate(VI). Chemosphere 90:2013–2019CrossRefGoogle Scholar
  20. Khundzhua DA, Patsaeva SV, Terekhova VA, Yuzhakov VI (2013) Spectral characterization of fungal metabolites in aqueous medium with humus substances. J Spectroscopy. doi: 10.1155/2013/.538608 Google Scholar
  21. Kononova MM (1966) Soil organic matter, its nature, its role in soil formation and in soil fertility. Pergamon, OxfordGoogle Scholar
  22. Kumke MU, Specht CH, Brinkmann T, Frimmel FH (2001) Alkaline hydrolysis of humic substances—spectroscopic and chromatographic investigations. Chemosphere 45(6–7):1023–1031CrossRefGoogle Scholar
  23. Lamar RT, Olk DC, Mayhew L, Bloom PR (2014) A new standardized method for quantification of humic and fulvic acids in humic ores and commercial products. J AOAC Int 97(3):721–730CrossRefGoogle Scholar
  24. Lobartini JC, Tan KH, Rema JA, Gingle AR, Pape C, Himmelsbach DS (1992) The geochemical nature and agricultural importance of commercial humic matter. Sci Total Environ 113:1–15CrossRefGoogle Scholar
  25. Lu XQ, Hanna JV, Johnson WD (2000) Source indicators of humic substances: an elemental composition, solid state 13C CP/MAS NMR and Py-GC/MS Study. Appl Geochem 15:1019–1033CrossRefGoogle Scholar
  26. Malcolm RL, MacCarthy P (1986) Limitations in the use of commercial HA in water and soil research. Environ Sci Technol 20:904–911CrossRefGoogle Scholar
  27. Miano TM, Senesi N (1992) Synchronous excitation fluorescence spectroscopy applied to soil humic substances chemistry. Sci Total Environ 117–118:41–51CrossRefGoogle Scholar
  28. Miano TM, Sposito G, Martin JP (1988) Fluorescence spectroscopy of humic substances. Soil Sci Soc Am J 52:1016–1019CrossRefGoogle Scholar
  29. Mobed JJ, Hemmingsen SL, Autry JL, McGown LB (1996) Fluorescence characterization of IHSS humic substances: total luminescence spectra with absorbance correction. Environ Sci Technol 30:3061–3065CrossRefGoogle Scholar
  30. Orlov DS (1995) Humic substances of soils and general theory of humification. Oxford & IBH Publishing, New DelhiGoogle Scholar
  31. Patsayeva S, Reuter R (1995) Spectroscopic study of major components of dissolved organic matter naturally occurring in water. Proc SPIE 2586: Global Process Monitoring and Remote Sensing of the Ocean and Sea Ice, pp. 151--160Google Scholar
  32. Patsayeva SV, Fadeev VV, Filippova EM, Yuzhakov VI (1991) Temperature and laser ultraviolet radiation influence on luminescence spectra of dissolved organic matter. Vestnik Moskovskogo Universiteta Seriya 3 Fizika Astronomiya 32(6):71–75Google Scholar
  33. Patsayeva SV, Fadeev VV, Filippova EM, Yuzhakov VI (1992) The fluorescence saturation effect of dissolved organic matter. Vestnik Moskovskogo Universiteta Seriya 3 Fizika Astronomiya 33(5):38–42Google Scholar
  34. Perminova IV, Kulikova NA, Zhilin DM, Grechischeva NY, Kovalevskii DV, GF L, DN M, PS V, AI K, VA K, VS P (2006) Mediating effects of humic substances in the contaminated environments. Concepts, results, and prospects. In: Twardowska I, Allen HE, Häggblom MM, Stefaniak S (eds) Viable methods of soil and water pollution monitoring, protection and remediation, NATO Science Series: IV, vol 69. Springer, Dordrecht, pp. 249–274CrossRefGoogle Scholar
  35. PerminovaYV HK, Hertkorn N (2005) Remediation chemistry of humic substances: theory and implications for technology. In: Perminova IV, Hatfield K, Hertkorn N (eds) Use of humic substances to remediate polluted environments: from theory to practice. Springer, Dordrecht, pp. 3–36CrossRefGoogle Scholar
  36. Peuravuori J, Pihlaja K (1997) Molecular size distribution and spectroscopic properties of aquatic humic substances. Anal Chim Acta 337:133–149CrossRefGoogle Scholar
  37. Poloskin RB, Gladkov OA, Osipova OA, Yakimenko OS (2012) Comparable evaluation of biological activity of new liquid and dry modifications of the humic product “Lignohumate”. In: Xu J, Wu J, He Y (eds) Functions of natural organic matter in changing environment, Springer, Beijing pp 1095–1099Google Scholar
  38. Pukalchik MA, Terekhova VA, Yakimenko OS, Kydralieva KA, Akulova MI (2015) Triad method for assessing the remediation effect of humic preparations on urbanozems. Euras Soil Sci 48:654–663CrossRefGoogle Scholar
  39. Saab SC, Martin-Neto L (2007) Condensed aromatic rings and E4/E6 ratio: humic acids in gleysoils studied by NMR CP/MAS 13C, and dipolar dephasing. Quim Nov. 30:260–263Google Scholar
  40. Senesi N, D’Orazio V (2005) Encyclopedia of soils in the environment Elsevier. In: Hillel D (ed) Fluorescence spectroscopy, pp. 35–52Google Scholar
  41. Senesi N, Miano TM, Provenzano MR, Brunetti G (1991) Characterization, differentiation, and classification of humic substances by fluorescence spectroscopy. Soil Sci 152:259–271CrossRefGoogle Scholar
  42. Shubina D, Fedoseeva E, Gorshkova O, Patsaeva S, Terekhova V, Timofeev M, Yuzhakov V (2010) The “blue shift” of emission maximum and the fluorescence quantum yield as quantitative spectral characteristics of dissolved humic substances. EARSeL eProc 9(1):13–21Google Scholar
  43. Sierra MMD, Donard OFX, Lamotte M, Belin C, Ewald M (1994) Fluorescence spectroscopy of coastal and marine waters. Mar Chem 47 (2):127--144Google Scholar
  44. Sierra MMD, Giovanela M, Parlanti E, Soriano-Sierra E (2005) Fluorescence fingerprint of fulvic and humic acids from varied origins as viewed by single-scan and excitation/emission matrix techniques. Chemosphere 58:715–733CrossRefGoogle Scholar
  45. Sorkina TA, Polyakov AY, Kulikova NA, Goldt AE, Philippova OI, Aseeva AA, Veligzhanin AA, ZubavichusYV, DA P, Goodilin EA, Perminova IV (2014) Nature-inspired soluble iron-rich humic compounds: new look at the structure and properties. J Soils Sediments 14:261–268CrossRefGoogle Scholar
  46. Stedmon C, Markager S (2001) The optics of chromophoric dissolved organic matter (CDOM) in the Greenland Sea: an algorithm for differentiation between marine and terrestrially derived organic matter. Limnol Oceanogr 46:2087–2093CrossRefGoogle Scholar
  47. Stevenson FJ (1994) Humus chemistry: genesis, composition, reactions. John Wiley and Sons, New YorkGoogle Scholar
  48. Tan KH (2003) Humic matter in soil and the environment: principles and controversies. Marcel Dekker, New YorkCrossRefGoogle Scholar
  49. Trubetskoj OA, Trubetskaya OE, Guyot G, Andreux F, Richard C (2002) Fluorescence of soil humic acids and their fractions obtained by tandem SEC-PAGE. Organic Geochem 33:213–220CrossRefGoogle Scholar
  50. Uyguner CS, Bekbolet M (2005) Evaluation of humic acid photocatalytic degradation by UV–vis and fluorescence spectroscopy. Catal Today 101(3):267–274CrossRefGoogle Scholar
  51. Weishaar JL, Aiken GR, Bergamaschi BA, Fram MS, Fujii R, Mopper K (2003) Evaluation of Specific Ultraviolet Absorbance as an Indicator of the Chemical Composition and Reactivity of Dissolved Organic Carbon. Environ Sci Technol 37 (20):4702--4708Google Scholar
  52. Yakimenko OS, Terekhova VA (2011) Humic preparations and the assessment of their biological activity for certification purposes. Eurasian Soil Sci 44:1222–1230CrossRefGoogle Scholar
  53. Zaccone C, Cocozza C, D’Orazio V, Plaza C, Cheburkin A, Miano TM (2007) Influence of extractant on quality and trace elements content of peat humic acids. Talanta 73:820–830CrossRefGoogle Scholar
  54. Zbytniewski R, Buszewski B (2005) Characterization of natural organic matter (NOM) derived from sewage sludge compost. Part 1: chemical and spectroscopic properties. Bioresource Technol 96:471–478CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2016

Authors and Affiliations

  • Olga Yakimenko
    • 1
  • Daria Khundzhua
    • 2
  • Aleksei Izosimov
    • 1
  • Viktor Yuzhakov
    • 2
  • Svetlana Patsaeva
    • 2
  1. 1.Department of Soil SciencesM.V. Lomonosov Moscow State UniversityMoscowRussia
  2. 2.Department of PhysicsM.V. Lomonosov Moscow State UniversityMoscowRussia

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